EP0123907B1 - Fluoropyrimidine derivatives - Google Patents

Fluoropyrimidine derivatives Download PDF

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Publication number
EP0123907B1
EP0123907B1 EP84103419A EP84103419A EP0123907B1 EP 0123907 B1 EP0123907 B1 EP 0123907B1 EP 84103419 A EP84103419 A EP 84103419A EP 84103419 A EP84103419 A EP 84103419A EP 0123907 B1 EP0123907 B1 EP 0123907B1
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EP
European Patent Office
Prior art keywords
liquid crystal
compounds
fluorophenyl
pyrimidine
alkyl
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Expired
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EP84103419A
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German (de)
French (fr)
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EP0123907A2 (en
EP0123907A3 (en
Inventor
Yasuyuki Goto
Tetsuya Ogawa
Kisei Kitano
Masahiro Fukui
Shigeru Sugimori
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JNC Corp
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Chisso Corp
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Priority claimed from JP5669283A external-priority patent/JPS59184165A/en
Priority claimed from JP9114883A external-priority patent/JPS59216876A/en
Priority claimed from JP16067183A external-priority patent/JPS6054371A/en
Application filed by Chisso Corp filed Critical Chisso Corp
Publication of EP0123907A2 publication Critical patent/EP0123907A2/en
Publication of EP0123907A3 publication Critical patent/EP0123907A3/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/34Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458Uncondensed pyrimidines
    • C09K19/3469Pyrimidine with a specific end-group other than alkyl, alkoxy or -C*-

Definitions

  • This invention relates to fluoropyrimidine derivatives and liquid crystal compositions containing the same.
  • Liquid crystal display elements utilize the optical anisotropy and the dielectric anisotropy of liquid crystal substances, and are classified into those of various modes such as TN type (twisted nematic type), DS type (dynamic scattering type), guest-host type, DAP type, etc. depending on their display modes, and the properties of liquid crystal substances suitable to the respective uses vary. It is common to any of liquid crystal substances that they are stable to moisture, air, heat, light, etc., and having a mesomorphic range as broad as possible, around room temperature, have been sought. Up to the present, however, any single compound which satisfies such conditions has not been found; hence liquid crystal compositions obtained by blending several kinds of liquid crystal compounds and non-liquid crystal compounds have been used.
  • liquid crystal compositions used for display elements that not only they should have a broad mesomorphic range including practical temperatures, but also they should have low viscosities, and further they should impart to display devices, low threshold voltages, short response times, and small electric power consumption.
  • GB-PS 1,473,990 discloses 5-alkyl-2-(4-cyanophenyl)pyrimidines as liquid crystal compounds having a high dielectric anisotropy, but even these compounds do not satisfy all of the above conditions required as a material for liquid crystal display elements.
  • EP-A-69 387 describes nematic liquid crystal materials, where among others phenylpyrimidine derivatives, the phenyl being substituted by a halogen atom or a cyano group, are described.
  • the object of the present invention is to provide novel compounds which, when added to liquid crystal substances, can improve some characteristics required for the resulting liquid crystal compositions.
  • fluoropyrimidine derivatives expressed by the general formula (I) wherein R' represents an alkyl group of 1 to 10 carbon atoms and I represents 1 or 2; with the proviso that 2-p-fluorophenyl-5-n-heptyl pyrimidine, 2-p-fluorophenyl-5-n-nonyl pyrimidine, and 2-p-fluorophenyl-5-n-decyl pyrimidine are excluded.
  • the present invention resides in liquid crystal compositions containing fluoropyrimidines expressed by the generral formula (I) defined above.
  • 5-Alkyl-2-(4-fluorophenyl)pyrimidines wherein the alkyl group has more than 10 carbon atoms are undesirable since their effectiveness as a viscosity-reducing agent is small. Further, 5-alkyl-2-(4'-fluorobiphenylyl-4)pyrimidines wherein the alkyl group has a long chain of carbon atoms are not practical due to their high viscosity.
  • Compounds of the present invention have low viscosities. Particularly those of the formula (I) wherein I represents 1 have extrapolation values of viscosity at 20°C (extrapolation values at 20°C of mixtures thereof with liquid crystal compositions of trans-cyclohexane derivatives) as extremely low as 6 to 8 cp.
  • the compounds of the present invention expressed by the formula (I) wherein I represents 2 have an anisotropy of refractive index An of about 0.24 which is larger than those of known liquid crystal substances; thus when the compounds are used in a small amount, it is possible to obtain display elements having a superior contrast.
  • 5-Alkyl-2-(4'-fluorobiphenyl-4)pyrimidines of the present invention have high clearing points; thus they, when added, have an effectiveness of raising the clearing points of the resulting liquid crystal compositions.
  • the compounds of the present invention are stable; hence when they are used as a structural element of liquid crystal display elements, they are very advantageous. Still further the compounds of the present invention have a superior compatability; hence when they are blended with other nematic liquid crystals and liquid crystal compositions such as those of cyclohexanecarboxylic acid phenyl esters, benzoic acid phenyl esters, phenylmetadioxanes, cyclohexanecarboxylic acid cyclohexyl esters, Schiff's bases, azoxy compounds, etc., it is possible to notably improve the specific properties of the resulting liquid crystal compositions, as described above.
  • R' and I are as defined above.
  • a 4-fluorobenzonitrile or 4-fluoro-4'-cyanobiphenylyl (compound (II)) as a starting raw material is reacted with HCI gas in methyl alcohol solvent to obtain an imido ether hydrochloride derivative (compound (III)). which is then reacted with NH 3 gas in an alcohol solvent to obtain an amidine hydrochloride derivative (compound IV)), which is then subjected to condensation-cyclization reaction with an acrolein derivative (compound (V)) in the presence of a suitable basic catalyst such as metal alcoholate, NaOH, DBU (1,8-diazabicyclo[5.4.0]-7-undecene), etc. to obtain the objective compound (I).
  • a suitable basic catalyst such as metal alcoholate, NaOH, DBU (1,8-diazabicyclo[5.4.0]-7-undecene
  • Example 1 was repeated except that 4-fluorobenzamidine hydrochloride and ⁇ -propyl-0-dimethyl- aminoacrolein of Example 1 were replaced by other substituted benzamidine hydrochlorides and a-alkyl-a-dimethylaminoacroleins, to prepare compounds shown in Examples 2-11 of Table 1. The values of physical properties thereof are shown in Table 1 together with the results of Example 1.
  • the symbols C, S, N, and I represent the respective phases of crystal, smectic, nematic and isotropic liquids, and numeral figures following the symbol - represent transition points (°C) from the above phases to the right side phases. Further, the numerals inside * ( ) are values obtained by blending the compounds with a liquid crystal composition (a composition consisting of three compounds in Application example 2 described later) followed by extrapolation.
  • a liquid crystal composition consisting of
  • Example 1 When 5-propyl-2-(4-fluorophenyl)pyrimidine (15 parts by weight) of Example 1 as one of the compounds of the present invention was added to the above liquid crystal composition (85 parts by weight), the resulting liquid crystal composition had a mesomorphic range of -10° to 55°C; hence the temperature region on the lower temperature side was improved, and when the composition was sealed in the same TN cell of 10 ⁇ m thick as above, the threshold voltage and saturation voltage of the resulting cell were reduced down to 1.30 V and 1.83 V, respectively, and its viscosity was 23 cp at 20°C, that is, improved to a large extent.
  • a liquid crystal composition consisting of
  • Example 6 When 5-propyl-2-(4'-fluorobiphenylyl-4)pyrimidine (15 parts by weight) of Example 6 as one of the compounds of the present invention was added to the above liquid crystal composition (85 parts by weight), the resulting nematic liquid crystal composition had a N-I point of 65°C. When this liquid crystal composition was sealed in the above TN cell, the threshold voltage and saturation voltage of the resulting cell were 1.41 V and 1.90 V, respectively. This indicates that when the compound of the present invention is added, the clearing point is raised and the operation voltages are reduced.
  • the characteristics of the resulting liquid crystal compositions can be improved; hence their effectiveness is notable.

Description

  • This invention relates to fluoropyrimidine derivatives and liquid crystal compositions containing the same.
  • Liquid crystal display elements utilize the optical anisotropy and the dielectric anisotropy of liquid crystal substances, and are classified into those of various modes such as TN type (twisted nematic type), DS type (dynamic scattering type), guest-host type, DAP type, etc. depending on their display modes, and the properties of liquid crystal substances suitable to the respective uses vary. It is common to any of liquid crystal substances that they are stable to moisture, air, heat, light, etc., and having a mesomorphic range as broad as possible, around room temperature, have been sought. Up to the present, however, any single compound which satisfies such conditions has not been found; hence liquid crystal compositions obtained by blending several kinds of liquid crystal compounds and non-liquid crystal compounds have been used.
  • Namely it has generally been required for liquid crystal compositions used for display elements that not only they should have a broad mesomorphic range including practical temperatures, but also they should have low viscosities, and further they should impart to display devices, low threshold voltages, short response times, and small electric power consumption.
  • GB-PS 1,473,990 discloses 5-alkyl-2-(4-cyanophenyl)pyrimidines as liquid crystal compounds having a high dielectric anisotropy, but even these compounds do not satisfy all of the above conditions required as a material for liquid crystal display elements.
  • EP-A-69 387 describes nematic liquid crystal materials, where among others phenylpyrimidine derivatives, the phenyl being substituted by a halogen atom or a cyano group, are described.
  • Zeitschrift für Naturforschung, volume 33b, 1978 discloses on pages 433 to 438 cyanophenyl or bromophenyl substituted pyrimidine derivatives.
  • The non-prepublished document EP-A-0126 949 describes fluoropyrimidine derivatives which have been excluded by a disclaimer.
  • The object of the present invention is to provide novel compounds which, when added to liquid crystal substances, can improve some characteristics required for the resulting liquid crystal compositions.
  • The above object is solved according to the invention by fluoropyrimidine derivatives expressed by the general formula (I)
    Figure imgb0001
    wherein R' represents an alkyl group of 1 to 10 carbon atoms and I represents 1 or 2; with the proviso that 2-p-fluorophenyl-5-n-heptyl pyrimidine, 2-p-fluorophenyl-5-n-nonyl pyrimidine, and 2-p-fluorophenyl-5-n-decyl pyrimidine are excluded.
  • Further, the invention has the following embodiments:
    • 5-Alkyl-2-(4-fluorophenyl)pyrimidines encompassed by the general formula (I), wherein I represents 1 and R' represents a linear chain alkyl group of 1 to 8 carbon atoms, with the proviso that 2-p-fluorophenyl-5-n-heptyl pyrimidine is excluded.
    • 5-Alkyl-2-(4'-fluorobiphenyl-4)pyrimidines expressed by the general formula (I) wherein I represents 2 and R' represents a linear chain alkyl group of 1 to 8 carbon atoms.
  • As a further aspect, the present invention resides in liquid crystal compositions containing fluoropyrimidines expressed by the generral formula (I) defined above.
  • 5-Alkyl-2-(4-fluorophenyl)pyrimidines wherein the alkyl group has more than 10 carbon atoms are undesirable since their effectiveness as a viscosity-reducing agent is small. Further, 5-alkyl-2-(4'-fluorobiphenylyl-4)pyrimidines wherein the alkyl group has a long chain of carbon atoms are not practical due to their high viscosity.
  • Compounds of the present invention expressed by the formula (I) wherein I represents 2 have a large positive value of dielectric anisotropy (abbreviated as As) As = ell ε wherein s represents a parallel dieletric constant and ε represents a perpendicular dielectric constant, and their As values are about +22.
  • Compounds of the present invention expressed by the formula (1) wherein I represents 1 have extrapolation values of As (extrapolation values from observed values of mixtures thereof with liquid crystal compositions of trans-cyclohexane derivatives) as considerably large as about +14.
  • Compounds of the present invention have low viscosities. Particularly those of the formula (I) wherein I represents 1 have extrapolation values of viscosity at 20°C (extrapolation values at 20°C of mixtures thereof with liquid crystal compositions of trans-cyclohexane derivatives) as extremely low as 6 to 8 cp.
  • Due to the above-mentioned specific properties, when the compounds of the present invention are added as a component, an effectiveness of reducing the viscosities of the resulting liquid crystal compositions and an effectiveness of reducing the threshold voltage of liquid crystal display elements obtained by the use of the compositions and improving the response velocity thereof are remarkable.
  • Further, the compounds of the present invention expressed by the formula (I) wherein I represents 2 have an anisotropy of refractive index An of about 0.24 which is larger than those of known liquid crystal substances; thus when the compounds are used in a small amount, it is possible to obtain display elements having a superior contrast.
  • 5-Alkyl-2-(4'-fluorobiphenyl-4)pyrimidines of the present invention have high clearing points; thus they, when added, have an effectiveness of raising the clearing points of the resulting liquid crystal compositions.
  • Further the compounds of the present invention are stable; hence when they are used as a structural element of liquid crystal display elements, they are very advantageous. Still further the compounds of the present invention have a superior compatability; hence when they are blended with other nematic liquid crystals and liquid crystal compositions such as those of cyclohexanecarboxylic acid phenyl esters, benzoic acid phenyl esters, phenylmetadioxanes, cyclohexanecarboxylic acid cyclohexyl esters, Schiff's bases, azoxy compounds, etc., it is possible to notably improve the specific properties of the resulting liquid crystal compositions, as described above.
  • The compounds of the present invention having such superior specific properties are prepared according to the following reactions:
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
  • In the above formulas, R' and I are as defined above.
  • First, a 4-fluorobenzonitrile or 4-fluoro-4'-cyanobiphenylyl (compound (II)) as a starting raw material is reacted with HCI gas in methyl alcohol solvent to obtain an imido ether hydrochloride derivative (compound (III)). which is then reacted with NH3 gas in an alcohol solvent to obtain an amidine hydrochloride derivative (compound IV)), which is then subjected to condensation-cyclization reaction with an acrolein derivative (compound (V)) in the presence of a suitable basic catalyst such as metal alcoholate, NaOH, DBU (1,8-diazabicyclo[5.4.0]-7-undecene), etc. to obtain the objective compound (I).
  • Preparation of the compounds (I) of the present invention and use examples thereof will be described below by way of Examples.
  • Example 1
  • Preparation of 5-propyl-2-(4-fluorophenyl)pyrimidine.
  • To a sodium methylate solution under agitation obtained by dissolving Na (2.8 g, 0.12 mol) in anhydrous methanol (20 c.c.) was added 4-fluorobenzamidine hydrochloride (10.5 g, 0.06 mol), followed by adding α-propyl-β-dimethylaminoacrolein (9.2 g. 0.06 mol), thereafter refluxing on heating for 3 hours with stirring, distilling off methanol under the atmospheric pressure after completion of the reaction, adding toluene (20 cc) to the reaction residue to extract the resulting product, washing the extraction liquid with water, drying with anhydrous sodium sulfate, distilling off toluene and recrystallizing the remaining oily substance from ethanol (20 c.c.) to obtain the objective 5-propyl-2-(4-fluorophenyl)pyrimidine (7.0 g). Yield: 55%. M.P. 52.7°C.
  • Examples 2-11
  • Example 1 was repeated except that 4-fluorobenzamidine hydrochloride and α-propyl-0-dimethyl- aminoacrolein of Example 1 were replaced by other substituted benzamidine hydrochlorides and a-alkyl-a-dimethylaminoacroleins, to prepare compounds shown in Examples 2-11 of Table 1. The values of physical properties thereof are shown in Table 1 together with the results of Example 1.
    Figure imgb0005
  • In Table 1, the symbols C, S, N, and I represent the respective phases of crystal, smectic, nematic and isotropic liquids, and numeral figures following the symbol - represent transition points (°C) from the above phases to the right side phases. Further, the numerals inside *( ) are values obtained by blending the compounds with a liquid crystal composition (a composition consisting of three compounds in Application example 2 described later) followed by extrapolation.
  • Application Example 1
  • A liquid crystal composition consisting of
    • trans-4-propyl-(4'-cyanophenyl)cyclohexane 26% by weight,
    • trans-4-pentyl-(4'-cyanophenyl)cyclohexane 36% by weight,
    • trans-4-heptyl-(4'-cyanophenyi)cyclohexane 25% by weight, and
    • trans-4-pentyi-(4"-cyanobiohenylyl-4)cyclohexane 13% by weight, has a nematic mesomorphic range of -5°C to 71.9°C. When this liquid crystal composition was sealed in a TN cell of 10 pm thick, the threshold voltage and saturation voltage of the resulting cell were 1.84 V and 2.43 V, respectively. Further, its viscosity was 27.9 cp at 20°C.
  • When 5-propyl-2-(4-fluorophenyl)pyrimidine (15 parts by weight) of Example 1 as one of the compounds of the present invention was added to the above liquid crystal composition (85 parts by weight), the resulting liquid crystal composition had a mesomorphic range of -10° to 55°C; hence the temperature region on the lower temperature side was improved, and when the composition was sealed in the same TN cell of 10 µm thick as above, the threshold voltage and saturation voltage of the resulting cell were reduced down to 1.30 V and 1.83 V, respectively, and its viscosity was 23 cp at 20°C, that is, improved to a large extent.
  • Application Example 2
  • A liquid crystal composition consisting of
    • trans-4-propyl-(4'-cyanophenyl)cyclohexane 30% by weight,
    • trans-4-pentyl-(4'-cyanophenyl)cyclohexane 40% by weight, and
    • trans-4-heptyl-(4'-cyanophenyl)cyclohexane 30% by weight, has a N-I point of 52.1°C. When this composition was sealed in a TN cell of 10 µm thick, the threshold voltage and saturation voltage of the resulting cell were 1.55 V and 2.15 V, respectively.
  • When 5-propyl-2-(4'-fluorobiphenylyl-4)pyrimidine (15 parts by weight) of Example 6 as one of the compounds of the present invention was added to the above liquid crystal composition (85 parts by weight), the resulting nematic liquid crystal composition had a N-I point of 65°C. When this liquid crystal composition was sealed in the above TN cell, the threshold voltage and saturation voltage of the resulting cell were 1.41 V and 1.90 V, respectively. This indicates that when the compound of the present invention is added, the clearing point is raised and the operation voltages are reduced.
  • As described above, when the compounds of the present invention are used, the characteristics of the resulting liquid crystal compositions can be improved; hence their effectiveness is notable.

Claims (4)

1. Fluoropyrimidine derivatives expressed by the general formula (I)
Figure imgb0006
wherein R' represents an alkyl group of 1 to 10 carbon atoms and I represents 1 or 2, with the proviso that 2-p-fluorophenyl-5-n-heptyl pyrimidine, 2-p-fluorophenyl-5-n-nonyl pyrimidine, and 2-p-fluoropheny-5-n-decyl pyrimidine are excluded.
2. 5-Alkyl-2-(4-fluorophenyl)pyrimidines according to Claim 1, expressed by the general formula
Figure imgb0007
wherein R' represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-octyl group.
3. 5-Alkyl-2-(4'-fluorobiphenylyl-4)-pyrimidines according to Claim 1, expressed by the general formula
Figure imgb0008
wherein R' represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl group.
4. A liquid crystal composition containing at least one member of fluoropyrimidine derivatives according to claim 1.
EP84103419A 1983-03-31 1984-03-28 Fluoropyrimidine derivatives Expired EP0123907B1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP5669283A JPS59184165A (en) 1983-03-31 1983-03-31 5-alkyl-2-(4-fluorophenyl)-pyrimidine
JP56692/83 1983-03-31
JP91148/83 1983-05-24
JP9114883A JPS59216876A (en) 1983-05-24 1983-05-24 Halogenopyrimidine derivative
JP160671/83 1983-09-01
JP16067183A JPS6054371A (en) 1983-09-01 1983-09-01 5-alkyl-2-(substituted phenyl)pyrimidine

Publications (3)

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EP0123907A2 EP0123907A2 (en) 1984-11-07
EP0123907A3 EP0123907A3 (en) 1985-10-23
EP0123907B1 true EP0123907B1 (en) 1989-07-26

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EP0123907A3 (en) 1985-10-23
US4581155A (en) 1986-04-08
DE3479120D1 (en) 1989-08-31

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